Process for making glycol ethers and glycol esters

ABSTRACT

GLYCOL ETHERS OR GLYCOL ESTERS HAVING THE FORMULA ROCMH2MZCNH2NOH ARE PREPARED BY REACTING A COMPOUND HAVING THE FORMULA ROH, A CYCLIC COMPOUND HAVING THE FORMULA CMH2MZ AND HAVING AT LEAST THREE AND NOT MORE THAN FIVE CARBON ATOMS IN THE RING AND A VICINAL ALKYLENE OXIDE HAVING THE FORMULA CNH2NO WHERE THE MOLAR RATIO OF CMH2MZ TO VICINAL OXIDE IS BETWEEN ONE TO TEN AND TEN TO ONE, THE MOLAR RATIO OF VICINAL OXIDE PLUS CMH2MZ TO ROH IS AT LEAST ONE TO ONE, R IS ACYL HAVING AT LEAST TWO AND NOT MORE THAN EIGHTEEN CARBON ATOMS OR ARYL HAVING UP TO TWO AROMATIC RINGS, Z IS OXYGEN OR SULFUR, M IS AN INTEGER OF FROM THREE TO FIFTEEN INCLUSIVE AND N IS AN INTEGER OF FROM TWO TO FOUR INCLUSIVE. THEY ARE USEFUL AS SOLVENTS, LUBRICANTS, HYDRAULIC FLUIDS AND CHEMICAL INTERMEDIATES.

United States Patent 3,577,559 PROCESS FOR MAKING GLYCOL ETHERS ANDGLYCOL ESTERS Lee H. Horsley, Midland, Mich., assignor to The DowChemical Company, Midland, Mich. No Drawing. Filed Jan. 19, 1968, Ser.No. 699,055 Int. Cl. C07c 69/76 US. Cl. 260410.6 11 Claims ABSTRACT OFTHE DISCLOSURE Glycol ethers or glycol esters having the formula ROC HZC H OH are prepared by reacting a compound having the formula ROH, acyclic compound having the formula C H Z and having at least three andnot more than five carbon atoms in the ring and a vicinal alkylene oxidehaving the formula C H O where the molar ratio of C H Z to vicinal oxideis between one to ten and ten to one, the molar ratio of vicinal oxideplus C H Z to ROH is at least one to one, R is acyl having at least twoand not more than eighteen carbon atoms or aryl having up to twoaromatic rings, Z is oxygen or sulfur, m is an integer of from three tofifteen inclusive and n1 is an integer of from two to four inclusive.They are useful as solvents, lubricants, hydraulic fluids and chemicalintermediates.

BACKGROUND OF THE INVENTION There is no known prior art concerning thereaction of a carboxylic or phenolic group, a vicinal alkene oxide and apoly-methylene cyclic ether (e.g. tetrahydrofuran) to give a glycolester or glycol ether containing the polymethylene cyclic ether moiety.

SUMMARY OF THE INVENTION It has now been found that glycol ethers orglycol esters having the formula ROC H ZC H OH are produced in goodyields by reacting a compound having the formula ROH, a cyclic compoundhaving the formula C H Z and having at least three and not more thanfive carbon atoms in the ring and a vicinal alkylene oxide having theformula C H O where the molar ratio of C H Z to vicinal oxide is betweenone to ten and ten to one and the molar ratio of vicinal oxide plus C HZ to ROH is at least one to one. In each of the above formulas, R isacyl having at least two and not more than eighteen carbon atoms(preferably having not more than eight carbon atoms) or aryl having upto two aromatic rings, Z is oxygen or sulfur, m is an integer of fromthree to fifteen inclusive and n is an integer of from two to fourinclusive.

In order to practice the invention, a compound having the formula ROH, acyclic compound having the formula C H Z and having at least three andnot more than five carbon atoms in the ring and a vicinal alkylene oxidehaving the formula C H O are reacted in any convenient manner, toproduce a glycol ether or glycol ester having the formula ROC H ZC H OHwherein the molar ratio of C H Z to vicinal oxide is between one to tenand ten to one and the molar ratio of vicinal oxide plus C H Z to ROH isat least one to one. The desired product is then removed from theproduct mixture by con- 3,577,559 Patented May 4, 1971 ventionalmethods. The products are useful as solvents, lubricants, hydraulicfluids and chemical intermediates.

The term acyl is meant to include radicals of aliphatic fatty acids suchas acetic, butyric, lauric, palmitic, stearic, acrylic, methacrylic,oleic, propiolic and the like. The term acyl is also meant to includeradicals of aromatic acids such as benzoic, toluic, phenylacetic,naphthoic, phthalic and the radicals of halo, alkoxy andaryloxy-substituted acyl groups. Examples of this latter class includelactic, diglycolic, phenoxyacetic, chlorobenzoic, bromobenzoic andanisic acid.

The term aryl is meant to include the aromatic monocyclic and dicyclicradicals, i.e., of the phenol and naphthol series. Of course, theseradicals may also contain inert substituents such as alkyl, aryl, halo,alkoxy and aryloxy. Examples of these substituted aromatics are 0-chlorophenol, iodonaphthol, methoxynaphthol, m-cresol andphenoxynaphthol.

Examples of vicinal oxides useful to this invention are ethylene oxide,propylene oxide, l-butene oxide and 2- butcne oxide. The cyclic compoundhaving the formula c n z must have at least three and not more than fivecarbon atoms in the ring. Examples of cyclic compounds useful in thisinvention are trimethylene oxide, tetrahydrofuran, pentamethylene oxide,tetrahydrothiophene and pentamethylene sulfide. Alkyl substitutedcyclics such as the 2-alkyl; 3-alkyl; 2,3-dialkyl; and similar alkylsubstituted cyclics are also suitable for use in this invention.Specific examples of these compounds are 2-butyl tetrahydrofuran,2,5-ethyl pentamethylene oxide and 2-ethyl pentamethylene sulfide.

The molar ratio of vicinal oxide plus C H Z to ROH should be at leastone to one and preferably at least three to one. Of course, higher molarratios may be employed without substantial effect on the invention.

The usual oxyalkylation catalysts may be used in this process, buthigher yields of the desired products are obtained without using acatalyst. Thus, the preferred method of operation is to conduct thereaction in the absence of a catalyst.

The temperature range employed is between and 200 C. and preferablybetween and 150 C. Lower temperatures give low reaction rates. Althoughautogenous pressure is preferred, higher pressures can suitably be used.

DESCRIPTION OF SPECIFIC EMBODIMENTS Below are specific examples of thepractice of our invention.

Example 1 A mixture of 0.01 mole of acetic acid, 0.02 mole of ethyleneoxide and 0.04 mole of tetrahydrofuran (Tl-IF) was sealed in a glasstube and heated at C. for 4 hours. The tube was cooled and opened.Analysis of the sample by titration showed 63 mole percent conversion ofthe acetic acid. The product after removal of the unreacted acid and theexcess ethylene oxide and THF consisted of 2.14 parts of ethylene glycolmonoacetate, 0.43 part of diethylene glycol monoacetate and 15 parts ofthe desired CH COO(CH OC H OH. This corresponds to 85% yield of thedesired product.

Using a similar procedure, the following results were obtained and arereported in Table I following.

TABLE I [Reaction of acids plus alkene oxides plus cyclic compound]Reactants Acid Oxide Cyclic compound Yield of Percent desired Run No.Type Moles Type Moles Type Moles 0. His conv. b product 01 E.O. 01 THF063 140 1 10.5 90. 6 01 E.O. 01 THE 063 140 4. 25 32 87. 2 01 13.0. 02THE 057 140 1 16 95.1 01 15.0. 02 THE 057 140 4. 25 61 85. 4 01 E.O. 04THF 045 140 1 32 86. 9 01 13.0. 04 THF 046 140 4. 25 71 79. 1 01 13.0.02 TH]? 02 140 4 85 71. 8 01 13.0. 01 THE 03 100 23 51. 44 82. 5 01 i-BO 03 THE 03 100 35 15. 6 01 i-B O 03 THF 03 100 20 31 54. 0 01 i-BO 03THF 03 100 20 57 28. 0 01 V E.() 03 THE 03 100 20 57 53. 1 01 E0. 03 TMO03 100 17. 5 83 84. 1 01 E.O. 03 PMO 03 100 17. 5 52 40.6 01 E.O. 03 THT03 100 17. 5 100 38. 0 01 E.O. 03 THF 03 140 4 99 44. 4 01 12.0. 03 THF03 140 4 99. 7 74. 7 01 E.O. 03 THF 03 140 3 93 50.0 01 P.O. 03 THE 03140 3 67 51. 6 01 P.O. 03 TMO 03 140 3 90 76. 4

THF =Tetrahydrofuan; HOAc=Acetic acid; E0. Ethylene oxide; i-B O=Isobutene oxide; V 13.0. Vinyl ethylene oxide; TMO Trimethylene oxide;PMO Pentamethylene oxide; THT Tetrahydrothiophene;

HOPr= Propiom'c acid; HOBZ= Benzoic acid.

b Percent conversion of acid starting material. 0 PercentROCmH2mZCnH2nOH produced based on acid converted.

EXAMPLE 2 A mixture of 0.01 mole of 2,4-dichlorophenol, 0.03 mole ofethylene oxide and 0.03 mole of tetrahydrofuran was sealed in a glasstube and heated for 4 hours at 140 C. The tube was cooled and opened foranalysis. Titration of a sample showed 51% conversion of the2,4-dichlorophenol. After removal of the unconverted phenol and excessethylene oxide and tetrahydrofuran there remained a mixture of 30.6parts of ethylene glycol mono-2,4-dichlorophenyl ether, 6.1 parts ofdiethylene glycol monodichlorophenyl ether and 63.3 parts of the desiredCl C H O (CH C H OH.

Using a similar procedure, the following results were obtained and arereported in Table II below. In each run, 0.01 mole of the phenol, 0.03mole of ethylene oxide and 0.03 mole of tetrahydrofuran were thereactants.

TABLE II [Reaction of phenols alkene oxide cyclic compound]p-Chlorophenol; 2,4-D=2,4-dichlorophenol; Penta=PentachlorophenoL bPercent ROOmHmQZOnHBnOH produced based on phenol converted. 55

I claim:

1. A process for making glycol ethers or glycol esters having theformula ROC H ZC H OH comprising reacting a compound having the formulaROH, a cyclic com pound having the formula c rr z and having at leastthree and not more than five carbon atoms in the ring and a vicinalalkylene oxide having the formula C H O where the molar ratio of C H Zto vicinal oxide is between one to ten and ten to one, the molar ratioof vicinal 65 oxide plus C H Z to ROH is at least one to one, R is acylderived from a carboxylic acid having at least two and not more thaneighteen carbon atoms or aryl having up to two aromatic rings, Z isoxygen or sulfur, m is an integer of from three to fifteen inclusive andn is an integer of from two to four inclusive.

2. A process as defined in claim 1 wherein the molar ratio of vicinaloxide plus C H Z to ROH is at least three to one.

3. A process as defined in claim 1 wherein the temperature is betweenand 200 C.

4. A process as defined in claim 1 wherein the temperature is betweenand C.

5. A process as defined in claim 1 wherein no catalyst is used.

6. A process as defined in claim 1 wherein R is a fatty acid radical ora phenol radical.

7. A process as defined in claim 1 wherein R is an aromatic acid radicalor a naphthol radical.

8. A process as defined in claim 1 wherein R is a halo, alkoxy, aryloxy,alkyl or aryl-substituted acyl or aryl group.

9. A process as defined in claim 1 wherein the vicinal oxide isethylene, propylene, l-butene or cis-Z-butene oxide.

10. A process as defined in claim 1 wherein the cyclic compound havingthe formula C H Z is trimethylene oxide, tetrahydrofuran orpentamethylene oxide.

11. A process as defined in claim 1 wherein the compound having theformula ROH is acrylic or methacrylic acid.

References Cited UNITED STATES PATENTS 2,314,454 3/1943 Manchen et a1.260496 2,819,296 1/1958 Carnes et a1. 260----486 3,206,486 9/1965 Nankees 260-4106 LORRAINE A. WEINBERGER, Primary Examiner R. S. WEISSBERG,Assistant Examiner US. Cl. X.R.

